连续流微反应器合成亚磷酸二甲酯的研究  

Studies on Continuous Flow Synthesis of Dimethyl Phosphite in Micro-Reactor

作　　者：刘建武[1] 严生虎[1] 张跃[1] Liu Jianwu;Yan Shenghu;Zhang Yue(School of Pharmaceutical and Life Sciences,Continuous Flow Engineering Laboratory of National Petroleum and Chemical Industry,Changzhou,Jiangsu 213164,China)

机构地区：[1]常州大学制药与生命科学学院石油和化工行业连续流技术工程实验室,江苏常州213164

出　　处：《化学世界》2021年第8期492-497,共6页Chemical World

基　　金：江苏省产学研前瞻性联合研究(No.BY2014037-19)资助项目。

摘　　要：以三氯化磷和甲醇为原料,在无溶剂的条件下,研究了在具有特殊微结构的金属微通道反应器中酯化合成亚磷酸二甲酯的连续流工艺。考察了n(三氯化磷)∶n(无水甲醇)比、反应温度和停留时间等因素对亚磷酸二甲酯合成的影响。最佳工艺结果为:n(三氯化磷)∶n(无水甲醇)=1∶3.2、反应温度30℃、停留时间3 min条件下,三氯化磷转化率为95.4%,亚磷酸二甲酯选择性为97.0%,亚磷酸二甲酯收率为92.6%。连续流金属高通量微通道反应器与间歇反应相比,具有停留时间短、强传质传热的特点,大大缩短了反应时间,提高了反应效率,解决了传统反应器由于反应剧烈、放热量大而带来的本质安全问题,实现了亚磷酸二甲酯的绿色安全高效合成。Dimethyl phosphite was synthesized by esterification under solvent-free conditions in a continuous flow metal micro-channel reactor with special micro-structure,using phosphorus trichloride and methanol as raw materials.The effects on the synthesis of dimethyl phosphite were investigated,including the ratio of materials,reaction temperature and residence time.The results showed that under the conditions of n(phosphorus trichloride)∶n(anhydrous methanol)=1∶3.2,reaction temperature at 30℃,residence time at 3 min,the conversion of PCl3 was 95.4%,the selectivity of dimethyl phosphate was 97.0%and the yield reached 92.6%.Compared to the batch reaction,the continuous flow metal micro-channel reaction has advantages of short residence time,strong mass transfer and heat transfer,which can greatly shorten the reaction time,improve the reaction efficiency and solve the intrinsic safety problem of traditional reactor due to violent reaction and large heat release,so that the green,safe and efficient synthesis of dimethyl phosphite was also realized.

关 键 词：无溶剂法 亚磷酸二甲酯 连续流 

分 类 号：TQ225[化学工程—有机化工]